MALDI-TOF mass spectrometry profiling of polar and nonpolar fractions in heated vegetable oils

Triacylglycerol oxidation of thermally stressed (6 h at 180 C, simulating deep-frying conditions) edible vegetable oil (sunflower and olive) was studied using matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS). Chromatographic separation of the nonpolar and polar components from the heated oil performed on silica gel prior to MS analysis significantly enhanced the detection of oxidized components. The spectra contained signals that were assigned to triacylglycerols (TAG), diacylglycerols (DAG), triacylglycerol oxidative dimers, oxidized TAG, and TAG fragments arising from the homolytic ?-scission of linoleyl, peroxy, and alkoxy radicals. Enrichment of the polar compounds prevented mass spectrometric ion suppression, thus allowing the detection of minor species originating from thermal oxidation. In addition, this allowed the monitoring of polar compounds in vegetable oils undergoing mild thermal treatment. As such, chromatographic separation coupled with MALDI-TOF MS analysis provided a rapid, sensitive, and specific tool to assess the thermal oxidation of vegetable oils.